Lithium bismuth oxide compounds as Li super-ionic conductor, solid electrolyte, and coating layer for Li metal battery and Li-ion battery

ABSTRACT

Solid-state lithium ion electrolytes of lithium potassium bismuth oxide based compounds are provided which contain an anionic framework capable of conducting lithium ions. Materials of specific formulae are provided and methods to alter the materials with inclusion of aliovalent ions shown. Lithium batteries containing the composite lithium ion electrolytes are provided. Electrodes containing the lithium borate based materials coated on the active material and batteries containing the electrodes are also provided.

THE NAMES OF THE PARTIES TO A JOINT RESEARCH AGREEMENT

The disclosure herein is a result of joint research effort conducted under a joint research agreement between TOYOTA MOTOR ENGINEERING & MANUFACTURING NORTH AMERICA, INC. having an address of 6565 Headquarters Drive W1-3C, Plano, Tex., 75024, and UNIVERSITY OF MARYLAND, COLLEGE PARK having an address of 2130 Mitchell Bldg. 7999 Regents Dr. College Park, Md., 20742.

FIELD OF THE DISCLOSURE

This disclosure is directed to novel lithium potassium bismuth oxide compounds useful as a Li super-ionic conductor, solid electrolytes containing the novel lithium potassium bismuth oxide compounds, and an electrode coating layer or component for a Li metal battery and a Li-ion battery containing the novel lithium potassium bismuth oxide compounds.

BACKGROUND

Li-ion batteries have traditionally dominated the market of portable electronic devices. However, conventional Li-ion batteries contain flammable organic solvents as components of the electrolyte and this flammability is the basis of a safety risk which is of concern and could limit or prevent the use of Li-ion batteries for application in large scale energy storage.

Replacing the flammable organic liquid electrolyte with a solid Li-ion conductive phase would alleviate this safety issue, and may provide additional advantages such as improved mechanical and thermal stability. A primary function of the solid conductive phase, usually called solid Li-ion conductor or solid state electrolyte, is to conduct Li⁺ ions from the anode side to the cathode side during discharge and from the cathode side to the anode side during charge while blocking the direct transport of electrons between electrodes within the battery.

Moreover, lithium batteries constructed with nonaqueous electrolytes are known to form dendritic lithium metal structures projecting from the anode to the cathode over repeated discharge and charge cycles. If and when such a dendrite structure projects to the cathode and shorts the battery energy is rapidly released and may initiate ignition of the organic solvent of the nonaqueous electrolyte.

Therefore, there is much interest and effort focused on the discovery of new solid Li-ion conducting materials which would lead to an all solid state lithium battery. Studies in the past decades have focused mainly on ionically conducting oxides such as for example, LISICON (Li₁₄ZnGe₄O₁₆), NASICON (Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄)₃), perovskite (for example, La_(0.5)Li_(0.5)TiO₃), garnet (Li₇La₃Zr₂O₁₂), LiPON (for example, Li_(2.88)PO_(3.73)N_(0.14)) and sulfides, such as, for example, Li₃PS₄, Li₇P₃S₁₁ and LGPS (Li₁₀GeP₂S₁₂).

While recent developments have improved the conductivity of solid Li-ion conductor to the level of 1-10 mS/cm, which is comparable to that in liquid phase electrolyte, finding new Li-ion solid state conductors is of great interest to further improve battery performance and safety.

An effective lithium ion solid-state conductor will have a high Li⁺ conductivity at room temperature. Generally, the Li⁺ conductivity should be no less than 10⁻⁶ S/cm. Further, the activation energy of Li⁺ migration in the conductor must be low for use over a range of operation temperatures that might be encountered in the environment. Additionally, the material should have good stability against chemical, electrochemical and thermal degradation. Unlike many conventionally employed non-aqueous solvents, the solid-state conductor material should be stable to electrochemical degradation reactivity with the anode and cathode chemical composition. The material should have low grain boundary resistance for usage in an all solid-state battery. Ideally, the synthesis of the material should be easy and the cost should not be high. Unfortunately, none of the currently known lithium ion solid electrolytes meet all these criteria. For example, Li₁₀GeP₂S₁₂ fails to meet the requirement of electrochemical stability and has a high cost due to the presence of Ge, despite its state-of-art Li conductivity. Environmentally stable composite materials having high Li⁺ conductivity and low activation energy would be sought in order to facilitate manufacturing methods and structure of the battery.

The standard redox potential of Li/Li+ is −3.04 V, making lithium metal one of the strongest reducing agents available, Consequently, Li metal can reduce most known cationic species to a lower oxidation state. Because of this strong reducing capability when the lithium metal of an anode contacts a solid-state Li⁺ conductor containing cation components different from lithium ion, the lithium reduces the cation specie to a lower oxidation state and deteriorates the solid-state conductor.

For example, the conductor of formula: Li₃PS₄ contains P⁵⁺ in the formula and is thus a secondary cation to the Li⁺. When in contact with Li metal, reduction according to the following equation occurs (J. Mater. Chem. A, 2016, 4, 3253-3266). Li₃PS₄+5Li→P+4Li₂S P+3Li→Li₃P

Similarly, Li₁₀GeP₂S₁₂ has also been reported to undergo degradation when in contact with lithium metal according to the following equations (J. Mater. Chem. A, 2016, 4, 3253-3266): Li₁₀GeP₂S₁₂+10Li→2P+8Li₂S+Li₄GeS₄ P+3Li→Li₃P 4Li₄GeS₄+31Li₂S+Li₁₅Ge₄ Li₁₀GeP₂S₁₂ contains Ge⁴⁺ and P⁵⁺ and each is reduced as indicated.

In another example, Li₇La₃Zr₂O₁₂, which contains secondary cations La³⁺ and Zr⁴⁺ undergoes chemical degradation when in contact with lithium metal according to the following chemistry (J. Mater. Chem. A, 2016, 4, 3253-3266): 6Li₇La₃Zr₂O₁₂+40Li→4Zr₃O+41Li₂O+9La₂O₃ Zr₃O+2Li→Li₂O+3Zr La₂O₃+6Li→2La+3Li₂O

Thus, many current conventionally known solid Li-ion conductors suffer a stability issue when in contact with a Li metal anode.

The inventors of this application have been studying lithium composite compounds which may serve for future use of solid-state Li+ conductors and previous results of this study are disclosed in U.S. application Ser. No. 15/626,696, filed Jun. 19, 2017, U.S. Ser. No. 15/805,672 filed Nov. 7, 2017, and U.S. application Ser. No. 16/013,495, filed Jun. 20, 2018. However, research effort continues to discover additional composites having maximum efficiency, high stability, low cost and ease of handling and manufacture.

Accordingly, an object of this application is to identify a range of further materials having high Li ion conductivity while being poor electron conductors which are suitable as a solid state electrolyte for a lithium ion battery and/or suitable as a protective coating layer for an electrode active material.

A further object of this application is to provide a solid state lithium ion battery and/or Lithium metal battery containing a solid state Li ion electrolyte membrane.

SUMMARY OF THE EMBODIMENTS

These and other objects are provided by the embodiments of the present application, the first embodiment of which includes a solid-state lithium ion electrolyte, comprising: at least one material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V): Li_(y)(M1)_(x1)KBiO₆  (I)

wherein x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)K_(1-x2)(M2)_(x2)BiO₆  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 and 17; Li_(y)KBi_(1-x3)(M3)_(x3)O₆  (III)

wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one element different from Bi selected from elements of groups 13, 14 and 15; Li_(y)KBiO_(6-x4)(X)_(x4)  (IV)

wherein x4 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and X is at least one element different from O selected from elements of groups 15, 16 and 17; and Li₆KBiO₆  (V).

In an aspect of the first embodiment the material of the solid state lithium ion electrolyte is of a trigonal crystal structure, an activation energy of the material is from 0.15 to 0.3 eV, and a lithium ion conductivity of the electrolyte is from 0.1 to 13.0 mS/cm at 300K.

In a second embodiment the present disclosure provides a solid state lithium battery, comprising: an anode; a cathode; and a solid state lithium ion electrolyte located between the anode and the cathode; wherein the solid state lithium ion electrolyte comprises at least one material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V): Li_(y)(M1)_(x1)KBiO₆  (I)

wherein x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)K_(1-x2)(M2)_(x2)BiO₆  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M2 is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 and 17; Li_(y)KBi_(1-x3)(M3)_(x3)O₆  (III)

wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one element different from Bi selected from elements of groups 13, 14 and 15; Li_(y)KBiO_(6-x4)(X)_(x4)  (IV)

wherein x4 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and X is at least one element different from O selected from elements of groups 15, 16 and 17; and Li₆KBiO₆  (V).

In special aspects of the second embodiment, the solid state lithium battery may be a lithium metal battery or a lithium ion battery.

In a third embodiment, the present disclosure provides an electrode having a current collector and an electrode active material on the current collector having a coating layer on a surface opposite the current collector of a material according to any of formulae (I) to (V), wherein formulae (I) to (V) are described in the previous embodiments.

Further, solid state batteries containing the electrodes of the third embodiment are provided.

The foregoing description is intended to provide a general introduction and summary of the present disclosure and is not intended to be limiting in its disclosure unless otherwise explicitly stated. The presently preferred embodiments, together with further advantages, will be best understood by reference to the following detailed description taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the crystal structure of Li₆KBiO₆.

FIG. 2 shows an Arrhenius plot of Li⁺ diffusivity D in Li₆KBiO₆ doped with Sn, Rh or Cr as indicated.

FIG. 3 shows the calculated X-ray Diffraction Analysis for Li₆KBiO₆ obtained based on Cu-Kα radiation with wavelength of 1.54184 Å.

FIG. 4 shows the position (2θ) and relative intensity of the peaks of the X-ray Diffraction Analysis for Li₆KBiO₆.

FIG. 5 shows a schematic diagram of the electrode according to one embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Throughout this description, the terms “electrochemical cell” and “battery” may be employed interchangeably unless the context of the description clearly distinguishes an electrochemical cell from a battery. Further the terms “solid-state electrolyte” and “solid-state ion conductor” may be employed interchangeably unless explicitly specified differently.

In the chemical formulae provided the term “less than” indicates less than the full value of the number stated. Thus, “less than” may mean a value up to 0.9 of the expressed number. For example, if the number indicated is 3, a number less than 3 may be 2.7. The term greater than 0 may mean a positive amount being present, such amount may be as little as 0.01.

Structural characteristics of effective Li⁺ conducting crystal lattices have been described by Ceder et al. (Nature Materials, 14, 2015, 1026-1031) in regard to known Li⁺ ion conductors Li₁₀GeP₂S₁₂ and Li₇P₃S₁₁, where the sulfur sublattice of both materials was shown to very closely match a bcc lattice structure. Further, Li⁺ ion hopping across adjacent tetrahedral coordinated Li⁺ lattice sites was indicated to offer a path of lowest activation energy.

The inventors are conducting ongoing investigations of new lithium compounds in order to identify materials having the properties which may serve as solid-state electrolytes in solid state lithium batteries. Such materials may also have utility as components of an electrode active material to improve capacity and/or cycling performance. Additionally and/or alternatively, such composite materials may be employed as protective coatings on an electrode active layer. In the course of this ongoing study and effort the inventors have developed and implemented a methodology to identify materials which have chemical and structural properties which have been determined by the inventors as indicators of lithium ion conductance suitable to be a solid state electrolyte for a lithium-ion battery.

To qualify as solid state electrolyte in practical applications, the material must meet several certain criteria. First, it should exhibit desirable Li-ion conductivity, usually no less than 10⁻⁶ S/cm at room temperature. Second, the material should have good stability against chemical, electrochemical and thermal degradation. Third, the material should have low grain boundary resistance for usage in all solid-state battery. Fourth, the synthesis of the material should be easy and the cost should not be high.

A criterion of this methodology requires that to qualify as solid state electrolyte in practical application, the material must exhibit desirable Li-ion conductivity, usually no less than 10⁻⁶ S/cm at room temperature. Thus, ab initio molecular dynamics simulation studies were applied to calculate the diffusivity of Li ion in the lattice structures of selected lithium metal sulfide materials. In order to accelerate the simulation, the calculation was performed at high temperatures and the effect of excess Li or Li vacancy was considered. In order to create excess Li or Li vacancy, aliovalent replacement of cation or anions may be evaluated. Thus, Li vacancy was created by, for example, partially substituting Si with aliovalent cationic species while compensating the charge neutrality with Li vacancy or excess Li. For example, replacing 50% of Si in Li₁₀Si₂PbO₁₀ with P results in the formation of Li₉PSiPbO₁₀.

The diffusivity at 300 K was determined according to equation (I) D=D ₀ exp(−E _(a) /k _(b) T)  equation (I) where D₀, E_(a) and k_(b) are the pre-exponential factor, activation energy and Boltzmann constant, respectively. The conductivity is related with the calculated diffusivity according to equation (II): σ=D ₃₀₀ ρe ² /k _(b) T  equation (II) where ρ is the volumetric density of Li ion and e is the unit charge.

The anionic lattice of Li-ion conductors has been shown to match certain lattice types (see Nature Materials, 14, 2015, 2016). Therefore, in the anionic lattice of the potential Li⁺ ion conductor is compared to the anionic lattice of Li⁺ ion conductor known to have high conductivity.

Thus, selected lithium potassium bismuth oxide compounds were compared to Li-containing compounds reported in the inorganic crystal structure database (FIZ Karlsruhe ICSD—https://icsd.fiz-karlsruhe.de) and evaluated in comparison according to an anionic lattice matching method developed by the inventors for this purpose and described in copending U.S. application Ser. No. 15/597,651, filed May 17, 2017, to match the lattice of these compounds to known Li-ion conductors.

Elements suitable for aliovalent substitution may be selected by an ionic substitution probability determined by the method as described by Hautier et al. (Inorg. Chem. 2011, 50, 656-663) wherein candidate dopants may be selected by an ionic substitution probabilistic model, constructed upon data mining of all known inorganic crystal materials. Dopants which could potentially create vacancies or interstitials within the particular materials were included. The structures with dopants that were not energetically favorable would be screened and excluded during phase stability calculations. The configurations of the sublattices, dopants, and vacancies or interstitials were determined by the computation methods described herein. Such methods have been described for example, in the following reports:

Bai et al., ACS Appl. Energy Materl 2018, 1, 1626-1634; and

He et al., Phys. Chem. Chem. Phys., 2015, 17, 18035.

According to the anionic lattice matching method described in copending U.S. application Ser. No. 15/597,651, an atomic coordinate set for the compound lattice structure may be converted to a coordinate set for only the anion lattice. The anions of the lattice are substituted with the anion of the comparison material and the obtained unit cell rescaled. The x-ray diffraction data for modified anion-only lattice may be simulated and an n×2 matrix generated from the simulated diffraction data. Quantitative structural similarity values be derived from the n×2 matrices.

The purpose of anionic lattice matching is to further identify compounds with greatest potential to exhibit high Li⁺ conductivity. From this work, the compounds described in the embodiments which follow were determined to be potentially suitable as solid-state Li⁺ conductors.

Ab initio molecular dynamics (AIMD) simulation was then applied to predict the conductivity of the targeted lithium aluminum borates. The initial structures were statically relaxed and were set to an initial temperature of 100 K. The structures were then heated to targeted temperatures (600-1200 K) at a constant rate by velocity scaling over a time period of 2 ps. The total time of AIMD simulations were in the range of 200 to 400 ps. Typical examples of the calculated diffusivity as a function of temperature are shown in FIG. 2 for samples of Li_(6.5)KBi_(0.5)Sn_(0.5)O₆, Li_(6.335)KBi_(0.665)Sn_(0.335)O₆, Li_(6.165)KBi_(0.835)Sn_(0.165)O₆, Li_(6.165)KBi_(0.835)Rh_(0.165)O₆ and Li_(6.335)KBi_(0.665)Cr_(0.335)O₆ where doping with Sn, Rh or Cr is shown. The Li⁺ diffusivity at different temperatures from 600-1200 K follows an Arrhenius-type relationship.

Applying equation (I) above the diffusivity at 300 K was determined and then the conductivity may be determined using the link between conductivity and diffusivity of equation (II). Table 1 shows the activation energy and room temperature conductivity determined for each of the samples of FIG. 2.

TABLE 1 Activation energy and room temperature conductivity of doped Li₃Al(BO₃)₂ from AIMD simulations. composition E_(a) (eV) σ (mS/cm) at 300K Li_(6.5)KBi_(0.5)Sn_(0.5)O₆ 0.18 11 Li_(6.335)KBi_(0.665)Sn_(0.335)O₆ 0.19 8 Li_(6.165)KBi_(0.835) Sn_(0.165)O₆ 0.27 0.33 Li_(6.165)KBi_(0.835)Rh_(0.165)O₆ 0.19 7 Li_(6.335)KBi_(0.665)Cr_(0.335)O₆ 0.19 13

As indicated, all of the compounds have conductivities above 0.1 mS/cm, thus meeting one of the requirements to be suitable as a solid Li-ion conductor.

Accordingly, the first embodiment provides a solid-state lithium ion electrolyte, comprising: at least one material selected from the group of compounds of formulae (I), (II), (III) and (IV): Li_(y)(M1)_(x1)KBiO₆  (I)

wherein x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)K_(1-x2)(M2)_(x2)BiO₆  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 and 17; Li_(y)KBi_(1-x3)(M3)_(x3)O₆  (III)

wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one element different from Bi selected from elements of groups 13, 14 and 15; and Li_(y)KBiO_(6-x4)(X)_(x4)  (IV)

wherein x4 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and X is at least one element different from O selected from elements of groups 15, 16 and 17.

The materials of formulae (I) to (IV) are doped materials of the compound of formula (V): Li₆KBiO₆  (V) wherein at least one of Li, K, Bi and O are aliovalently replaced as described above. The inventors have learned that the resulting doped materials retain the crystal structure of the base compound and have activation energies and conductivity related to the base compound of formula (V). Based on the measurement methods described above the lithium ion (Li⁺) conductivity of the solid state lithium ion electrolytes of formulae (I) to (V) is from 0.1 to 13.0 mS/cm at 300K, the activation energy of the composite of formula (IV) is 0.15 to 0.3 eV, and the composite of formula (V) comprises a crystal lattice structure having a trigonal crystal structure.

A calculated X-ray diffraction analysis for Li₆KBiO₆ obtained based on Cu-Kα radiation with wavelength of 1.54184 Å is shown in FIG. 3 and the location (2θ) and relative intensities of the major peaks is shown in FIG. 4.

Synthesis of the materials of the embodiments described above may be achieved by solid state reaction between stoichiometric amounts of selected precursor materials. Exemplary methods of solid state synthesis are described for example in each of the following papers: i) Monatshefte für Chemie, 100, 295-303, 1969; ii) Journal of Solid State Chemistry, 128, 1997, 241; iii) Zeitschrift für Naturforschung B,50,1995, 1061; iv) Journal of Solid State Chemistry 130, 1997, 90; v) Journal of Alloys and Compounds, 645, 2015, 5174; and vi) Z. Naturforsch. 51b, 199652 5. Exemplary methods of synthesis of bismuth metal oxides are described in K. Kumada et al., Mater. Res. Bull., 32, 1003-8 (1997); K. Kumada et al., Solid State Ionics, 122, 183-9(1999); D. E. Cox & A. W. Sleight, Solid State Commun., 19, 969-973 (1976); and O. Knop et al., Can. J. Chem., 58, 2221-4 (1980). Adaptation of these methods to prepare the compounds according to the embodiments disclosed herein is well within the capability of one of ordinary skill in the art.

In further embodiments, the present application includes solid state lithium ion batteries containing the solid-state electrolytes described above. Solid-state batteries of these embodiments including metal-metal solid-state batteries may have higher charge/discharge rate capability and higher power density than classical batteries and may have the potential to provide high power and energy density.

Thus, in further embodiments, solid-state batteries comprising: an anode; a cathode; and a solid state lithium ion electrolyte according to the embodiments described above, located between the anode and the cathode are provided.

The anode may be any anode structure conventionally employed in a lithium ion battery or lithium metal battery. Generally such materials are capable of insertion and extraction of Li⁺ ions. Example anode active materials may include graphite, hard carbon, lithium titanate (LTO), a tin/cobalt alloy and silicon/carbon composites. In one aspect the anode may comprise a current collector and a coating of a lithium ion active material on the current collector. Standard current collector materials include but are not limited to aluminum, copper, nickel, stainless steel, carbon, carbon paper and carbon cloth. In an aspect advantageously arranged with the solid-state lithium ion conductive materials described in the first and second embodiments, the anode may be lithium metal or a lithium metal alloy, optionally coated on a current collector. In one aspect, the anode may be a sheet of lithium metal serving both as active material and current collector.

The cathode structure may be any conventionally employed in lithium ion batteries, including but not limited to composite lithium metal oxides such as, for example, lithium cobalt oxide (LiCoO₂), lithium manganese oxide (LiMn₂O₄), lithium iron phosphate (LiFePO₄) and lithium nickel manganese cobalt oxide. Other active cathode materials may also include elemental sulfur and metal sulfide composites. The cathode may also include a current collector such as copper, aluminum and stainless steel.

In one aspect, the active cathode material may be a transition metal, preferably, silver or copper. A cathode based on such transition metal may not include a current collector.

In a further set of embodiments, electrodes for solid state lithium batteries containing the solid electrolyte composites of formulae (I) to (V) are also provided.

Thus the present disclosure provides an electrode for a solid state lithium battery, comprising: a current collector; and an electrode active layer on the current collector; wherein the electrode active layer comprises a composite compound of at least one composite material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V): Li_(y)(M1)_(x1)KBiO₆  (I)

wherein x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)K_(1-x2)(M2)_(x2)BiO₆  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 12, 13, 14, 16 and 17; Li_(y)KBi_(1-x3)(M3)_(x3)O₆  (III)

wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one element different from Bi selected from elements of groups 13, 14 and 15; Li_(y)KBiO_(6-x4)(X)_(x4)  (IV)

wherein x4 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and X is at least one element different from O selected from elements of groups 15, 16 and 17; and Li₆KBiO₆  (V).

In another embodiment, the present disclosure provides an electrode for a solid state lithium battery, comprising: a current collector; and an electrode active layer on the current collector; wherein the electrode active layer is coated on a surface opposite the current collector with a composition comprising a compound of at least one material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V): Li_(y)(M1)_(x1)KBiO₆  (I)

wherein x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)K_(1-x2)(M2)_(x2)BiO₆  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 and 17; Li_(y)KBi_(1-x3)(M3)_(x3)O₆  (III)

wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one element different from Bi selected from elements of groups 13, 14 and 15; Li_(y)KBiO_(6-x4)(X)_(x4)  (IV)

wherein x4 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and X is at least one element different from O selected from elements of groups 15, 16 and 17; and Li₆KBiO₆  (V).

In each of these electrode embodiments, the physical properties and other aspects described above for the solid state electrolyte are also applicable.

FIG. 5 shows a schematic drawing of the arrangement of elements in a general electrode according to the embodiment. Component (10) is the current collector. Layer (20) on the current collector is the electrode active material. Surface (4) of the electrode active material which is opposite the side on the current collector is coated with layer (30) of the material according to formulae (I) to (V).

Thus, in the preparation of the electrode the active material as described above may be physically mixed with the solid electrolyte material before application to the current collector or the solid electrolyte material may be applied as a coating layer on the exposed surface of the active material which has been applied onto the current collector. In either embodiment the presence of the lithium ion super conductor on or within the electrode structure may enhance performance of the electrode, for example, by increase of capacity and/or charge/discharge cycling stability and especially when applied as a coating layer, may serve to protect a conventional solid state electrolyte. Further, such coating may serve to improve adhesion of the electrode surface with a solid state electrolyte.

Thus, an embodiment of the present disclosure includes a cathode comprising a current collector and a layer of cathode active material applied to the current collector wherein the layer of cathode active material applied to the current collector is coated on a surface opposite the current collector with a layer comprising at least one of the solid electrolyte materials of formulae (I) to (V).

In related embodiments the present disclosure includes an anode comprising a current collector and a layer of anode active material applied to the current collector wherein at least one of the following components is present: i) the anode active material applied to the current collector is a physical mixture containing at least one of the solid electrolyte composites of formulae (I) to (V) as described above; and ii) the layer of anode active material applied to the current collector is coated with a layer comprising at least one of the solid electrolyte composites of formulae (I) to (V).

Batteries containing a cathode as described in the above embodiments, an anode described in the above embodiment or containing both an anode and cathode according to the above embodiments are also embodiments of the present disclosure.

The above description is presented to enable a person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the invention. Thus, this invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. In this regard, certain embodiments within the invention may not show every benefit of the invention, considered broadly. 

The invention claimed is:
 1. A solid-state lithium ion electrolyte, comprising: at least one material selected from the group of compounds of formulae (I), (II), (III) and (IV): Li_(y)(M1)_(x1)KBiO₆  (I) wherein x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one metal different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)K_(1-x2)(M2)_(x2)BiO₆  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is at least one metal different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)Bi_(1-x3)(M3)_(x3)O₆  (III) wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one metal different from Bi selected from elements of groups 13, 14 and 15; and Li_(y)KBiO_(6-x4)(X)_(x4)  (IV) wherein x4 is a number from greater than 0 to less than 6, y is a value: such that charge neutrality of the formula is obtained, and X is at least one element different from 0 selected from elements of groups 15, 16 and
 17. 2. The solid state lithium ion electrolyte according to claim 1, wherein the material of formulae (I)-(IV) is of a trigonal crystal structure, an activation energy of the composite is from 0.15 to 0.3 eV, and a lithium ion conductivity is from 0.1 to 13.0 mS/cm at 300K.
 3. The solid state lithium ion electrolyte according to claim 1, wherein an X-ray Diffraction (XRD) analysis of the material obtained based on Cu-Kα radiation with wavelength of 1,54184 Å comprises the following peaks which have a relative intensity to the highest intensity peak of at least 10%: Peak position Relative intensity 17.199 100.000  21.113 94.141 27.345 60.688 27.358 44.251 34.802 23.002 34.812 13.231 37.002 25.393 41.062 65.207 42.963 17.130 42.988 20.950 46.625 18.685 51.702 17.045 53.306 19.779 56.460 12.784 57.987 14.187 60.928 19.272 60.955  11.884.


4. A solid state lithium battery, comprising: an anode; a cathode; and a solid state lithium ion electrolyte located between the anode and the cathode; wherein the solid state lithium ion electrolyte comprises at least one material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V): Li_(y)(M1)_(x1)KBiO₆  (I) wherein x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one metal different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)K_(1-x2)(M2)_(x2)BiO₆  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is at least one metal different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 9, 10, 11, 12, and 13; Li_(y)KBi_(1-x3)(M3)_(x3)O₆  (III) wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one metal different from Bi selected from elements of groups 13, 14 and 15; Li_(y)KBiO_(6-x4)(X)_(x4)  (IV) wherein x4 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and X is at least one element different from O selected from elements of groups 15, 16 and 17; and Li₆KBiO₆  (V).
 5. The solid state lithium battery of claim 4, wherein the material of formulae (I)-(V) is of a trigonal crystal structure, an activation energy of the material is from 0.15 to 0.3 eV, and a lithium ion conductivity is from 0.1 to 13 mS/cm at 300K.
 6. The solid state lithium battery of claim 5, wherein an XRD analysis of the material obtained based on Cu-Kα radiation with wavelength of 1.54184 Å comprises the following peaks which have a relative intensity to the highest intensity peak of at least 10%: Peak position Relative intensity 17.199 100.000  21.113 94.141 27.345 60.688 27.358 44.251 34.802 23.002 34.812 13.231 37.002 25.393 41.062 65.207 42.963 17.130 42.988 20.950 46.625 18.685 51.702 17.045 53.306 19.779 56.460 12.784 57.987 14.187 60.928 19.272 60.955  11.884.


7. The solid state lithium battery of claim 4, wherein the battery is a lithium metal battery or a lithium ion battery.
 8. An electrode for a solid state lithium battery, comprising: a current collector; an electrode active layer on the current collector; and a coating on the surface of the electrode active layer opposite the current collector; wherein the coating is of a compound of at least one material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V): Li_(y)(M1)_(x1) KBiO₆  (I) wherein x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one metal different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13; Li_(y)K_(1-x2)(M2)_(x2) BiO₆  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is at least one metal different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and 13; Li_(y)KBi_(1-x3)(M3)_(x3)O₆  (III) wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one metal different from Bi selected from elements of groups 13, 14 and 15; Li_(y)KBiO_(6-x4)(X)_(x4)  (IV) wherein x4 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and X is at least one element different from O selected from elements of groups 15, 16 and 17; and Li₆KBiO₆  (V).
 9. The electrode for a solid state lithium battery of claim 8, wherein the material of formulae (I)-(V) is of a trigonal crystal structure, an activation energy of the material is from 0.15 to 0.3 eV, and a lithium ion conductivity of the material is from 0.1 to 13.0 mS/cm at 300K.
 10. A solid state lithium battery comprising at least one electrode according to claim 8, wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery. 